This invention is directed to radiography. In particular, it is directed to blue light-sensitive radiographic silver halide films that have high sensitivity and low residual spectral sensitizing dye stain. This invention also provides an imaging assembly and a method of radiographic imaging using these improved radiographic films.
The use of radiation-sensitive silver halide emulsions for medical diagnostic imaging can be traced to Roentgen""s discovery of X-radiation by the inadvertent exposure of a silver halide film. Eastman Kodak Company then introduced its first product specifically that was intended to be exposed by X-radiation in 1913. The discovery of X-rays in 1895 provided the beginning of a new way of providing medical evaluation and diagnosis. Prior to that time, medical examination comprised predominantly manual probing and consideration of symptoms. Such examinations would obviously be incomplete and inconclusive in most instances, and incorrect in some instances. In some cultures, there was a prohibition of touching the female anatomy, further limiting the effectiveness of medical examination. Thus, the discovery that X-radiation could pass through the body with relatively little harm and provide useful images provided a powerful tool in medical diagnosis and treatment.
In conventional medical diagnostic imaging the object is to obtain an image of a patient""s internal anatomy with as little X-radiation exposure as possible. The fastest imaging speeds are realized by mounting a dual-coated radiographic element between a pair of fluorescent intensifying screens for imagewise exposure. About 5% or less of the exposing X-radiation passing through the patient is adsorbed directly by the latent image forming silver halide emulsion layers within the dual-coated radiographic element. Most of the X-radiation that participates in image formation is absorbed by phosphor particles within the fluorescent screens. This stimulates light emission that is more readily absorbed by the silver halide emulsion layers of the radiographic element.
Examples of radiographic element constructions for medical diagnostic purposes are provided by U.S. Pat. No. 4,425,425 (Abbott et al.) and U.S. Pat. No. 4,425,426 (Abbott et al.), U.S. Pat. No. 4,414,310 (Dickerson), U.S. Pat. No. 4,803,150 (Dickerson et al.), U.S. Pat. No. 4,900,652 (Dickerson et al.), U.S. Pat. No. 5,252,442 (Tsaur et al.), and Research Disclosure, Vol. 184, August 1979, Item 18431.
Some commercial radiographic films that are available from Eastman Kodak Company and Agfa-Gevaert are sensitive to blue light and designed to be used in combination with blue-emitting fluorescent intensifying screens such as those containing calcium tungstate as the phosphor. Those films generally contain high silver coverage in the form of grains having cubic or other 3-dimensional morphology. The emulsion layers in those films are relatively xe2x80x9csoftxe2x80x9d meaning that relatively low levels of film hardener are used, in order to maximize covering power and to reduce drying time after processing with wet chemistries. However, the higher silver coverage contributed to longer processing times.
In addition, the silver halide emulsions in such films are generally xe2x80x9cinternally foggedxe2x80x9d meaning that the emulsion grains have internal latent image sensitivity. Such emulsions, when coated in combination with high silver iodide emulsions sufficient to release iodide upon development to render the internally fogged emulsion developable, results in higher covering power than would be possible with the silver iodide emulsions. This property can provide the advantage of lower silver coverage and improved processing compared to higher silver containing films, but it is also disadvantageous in that if the developer is contaminated with photographic fixers from the fixing tank, the internally fogged emulsion is developer prematurely and provided high fogging (Dmin).
Silver halide grains have a natural sensitivity to xe2x80x9cbluexe2x80x9d light, but in order to enhance their sensitivity for use in radiographic films, spectral sensitizing dyes are used to match the radiographic film to the emission of the blue-light emitting intensifying screens. Various blue light absorbing spectral sensitizing dyes are known for this purpose as described, for example, in U.S. Pat. No. 4,518,689 (Noguchi et al.).
However, there is a risk that after wet processing of the radiographic films, blue light absorbing sensitizing dyes may not be completely removed in the processing solutions, resulting in residual dye stain that can detract from the desired radiographic image. If the stain is too high, of course, the image may be useless for the intended diagnostic use. In addition, the incorrect selection of spectral sensitizing dyes may diminish photographic speed.
There is a desire in the industry to have xe2x80x9cblue-sensitivexe2x80x9d or xe2x80x9cblue-light sensitivexe2x80x9d radiographic films that have reduced silver coverage and reduced stain from residual spectral sensitizing dye without a significant loss of desired sensitometric properties.
The present invention provides a blue-sensitive radiographic silver halide film comprising a support having first and second major surfaces,
the radiographic silver halide film having disposed on the first major support surface, one or more hydrophilic colloid layers including a first silver halide emulsion layer, and on the second major support surface, one or more hydrophilic colloid layers including a second silver halide emulsion layer,
the first silver halide emulsion layer comprising predominantly tabular silver halide grains that have an aspect ratio of at least 15, a grain thickness of at least 0.1 xcexcm, and comprise at least 90 mol % bromide and up to 4 mol % iodide, based on total silver halide, substantially all of the iodide being present in an internal localized portion of the tabular silver halide grains that excludes the surface of the grains,
wherein the tabular silver halide grains in the first silver halide emulsion layer are dispersed in a hydrophilic polymeric vehicle mixture comprising at least 0.5% of oxidized gelatin, based on the total dry weight of the polymeric vehicle mixture, and
wherein the tabular silver halide grains in the first silver halide emulsion layer are spectrally sensitized with a combination of first and second spectral sensitizing dyes that has a maximum J-aggregate absorption on the tabular silver halide grains of from about 380 to about 500 nm, wherein the maximum J-aggregate absorption of the first spectral sensitizing dye is from about 20 to about 50 nm lower in wavelength than the maximum J-aggregate absorption of the second spectral sensitizing dye, the molar ratio of the first spectral sensitizing dye to the second spectral sensitizing dye being from about 0.25:1 to about 1:1, and the first and second spectral sensitizing dyes being present to provide from about 50 to 100% of saturation coverage of the tabular silver halide grains.
In preferred embodiments, the blue-sensitive, radiographic silver halide film of this invention comprises a support having first and second major surfaces,
the radiographic silver halide film having disposed on the first major support surface, one or more hydrophilic colloid layers including a first silver halide emulsion layer, and on the second major support surface, one or more hydrophilic colloid layers including a second silver halide emulsion layer,
the first and second silver halide emulsion layers having essentially the same composition and comprising predominantly tabular silver halide grains that have an aspect ratio of from about 20 to about 30, a grain thickness of from about 0.10 to about 0.14 xcexcm, and comprising at least 95 mol % bromide and from about 1 to about 3.5 mol % iodide, based on total silver halide in each of the emulsion layers, substantially all of the iodide being present in an internal localized portion of the tabular silver halide grains that from about 1.7 to about 85% of the volume of the grains wherein 100% volume represents the surface of the grains,
wherein the tabular silver halide grains in the first and second silver halide emulsion layers are dispersed in a hydrophilic polymeric vehicle mixture comprising from about 0.8% to about 1.2% of deionized oxidized gelatin, based on the total dry weight of the polymeric vehicle mixture, and
wherein the tabular silver halide grains in the first and second silver halide emulsion layers are spectrally sensitized with a combination of first and second spectral sensitizing dyes that has a maximum J-aggregate absorption on the tabular silver halide grains of from about 410 to about 490 nm, wherein the maximum J-aggregate absorption of the first spectral sensitizing dye is from about 30 to about 45 nm lower in wavelength than the maximum J-aggregate absorption of said second spectral sensitizing dye, the molar ratio of the first spectral sensitizing dye to the second spectral sensitizing dye being from about 0.5:1 to about 1:1, and the first and second spectral sensitizing dyes being present to provide from about 70 to about 80% of saturation coverage of the tabular silver halide grains in both silver halide emulsion layers,
the first spectral sensitizing dye being one of the following dyes I-1 through I-11 shown below, and the second spectral sensitizing dye being one of the following dyes II-1 through II-11 shown below.
In addition, this invention provides a photosensitive silver halide emulsion comprising predominantly tabular silver halide grains that have an aspect ratio of at least 15, a grain thickness of at least 0.1 xcexcm, and comprise at least 90 mol % bromide and up to 4 mol % iodide, based on total silver halide, substantially all of the iodide being present in an internal localized portion of the tabular silver halide grains that excludes the surface of the grains,
wherein the tabular silver halide grains are dispersed in a hydrophilic polymeric vehicle mixture comprising at least 0.3 g and up to 27 g of oxidized gelatin per mole of silver in the emulsion, and
wherein the tabular silver halide grains are spectrally sensitized with a combination of first and second spectral sensitizing dyes that has a maximum J-aggregate absorption on the tabular silver halide grains of from about 380 to about 500 nm, wherein the maximum J-aggregate absorption of the first spectral sensitizing dye is from about 20 to about 50 nm lower in wavelength than the maximum J-aggregate absorption of the second spectral sensitizing dye, the molar ratio of the first spectral sensitizing dye to the second spectral sensitizing dye being from about 0.25:1 to about 1:1, and the first and second spectral sensitizing dyes being present to provide from about 50 to 100% of saturation coverage of the tabular silver halide grains.
This invention also provides a radiographic imaging assembly comprising:
A) the blue-sensitive, radiographic silver halide film of this invention as described herein, and
B) a fluorescent intensifying screen that comprises an inorganic phosphor capable of absorbing X-rays and emitting electromagnetic radiation having a wavelength of from about 360 to about 540 nm, the inorganic phosphor being coated in admixture with a polymeric binder in a phosphor layer onto a flexible support and having a protective overcoat disposed over the phosphor layer.
Further, this invention provides a method of providing a black-and-white image comprising exposing the radiographic imaging assembly of this invention, and processing the blue-sensitive radiographic silver halide film, sequentially, with a black-and-white developing composition and a fixing composition, the processing being carried out within 90 seconds, dry-to-dry.
In addition, a method of providing a black-and-white image comprises exposing the blue-sensitive radiographic silver halide film of this invention, and processing the blue-sensitive radiographic silver halide film, sequentially, with a black-and-white developing composition and a fixing composition, the processing being carried out within 90 seconds, dry-to-dry.
The present invention provides an improved blue-sensitive, radiographic film with relatively lower silver coverage than known films and reduced stain from residual spectral sensitizing dyes without significant loss in sensitometric properties such as speed and maximum density. In fact, the photographic speed of the film is actually increased.
These advantages are achieved by a combination of properties in the radiographic film emulsions. Thus, the emulsions contain high aspect tabular grains that have a thickness of at least 0.1 xcexcm and include up to 4 mol % iodide based on total silver. This iodide is in localized portions of the grains that do not include the grain surface or the most internal nucleated and early-growth portions of the grains. In addition, the coated tabular grains are dispersed in a hydrophilic polymeric binder mixture that includes at least 0.5 weight % of oxidized gelatin based on the total dry weight of the polymeric vehicle mixture. The emulsion formulation used to make the coated silver halide emulsion layer is similar in composition except that the level of oxidized gelatin is generally higher because additional polymer binders (such as non-oxidized gelatin) are usually added prior to coating. For example, the emulsion formulation can include at least 0.3 g of oxidized gelatin per mole of silver.
In addition, a combination of two classes of blue light absorbing spectral sensitizing dyes are used that expectedly provides increased photographic speed and reduced residual dye stain after the radiographic films of this invention are wet processed. This combination of xe2x80x9cfirstxe2x80x9d and xe2x80x9csecondxe2x80x9d spectral sensitizing dyes has a maximum J-aggregate absorption on the tabular silver halide grains of from about 380 to about 500 nm, wherein the maximum J-aggregate absorption of the xe2x80x9cfirstxe2x80x9d spectral sensitizing dye is from about 20 to about 50 nm lower in wavelength than the maximum J-aggregate absorption of the xe2x80x9csecondxe2x80x9d spectral sensitizing dye. In addition, the molar ratio of the xe2x80x9cfirstxe2x80x9d spectral sensitizing dye to the xe2x80x9csecondxe2x80x9d spectral sensitizing dye is from about 0.25:1 to about 1:1, and the spectral sensitizing dyes are present to provide from about 50 to 100% of saturation coverage of the tabular silver halide grains.
The term xe2x80x9ccontrastxe2x80x9d as herein employed indicates the average contrast derived from a characteristic curve of a radiographic film using as a first reference point (1) a density (D1) of 0.25 above minimum density and as a second reference point (2) a density (D2) of 2.0 above minimum density, where contrast is xcex94D (i.e. 1.75)÷xcex94log10E (log10E2xe2x88x92log10E1), E1 and E2 being the exposure levels at the reference points (1) and (2).
xe2x80x9cGammaxe2x80x9d is described as the instantaneous rate of change of a D logE sensitometric curve or the instantaneous contrast at any loge value.
xe2x80x9cPhotographic speedxe2x80x9d for the radiographic silver halide films of this invention refers to the exposure necessary to obtain a density of at least 1.0 plus Dmin in the resulting black-and-white image.
Image tone (or dye stain) can be evaluated using conventional CIELAB (Commission Internationale de l""Eclairage) a* and b* values that can be evaluated using the techniques described by Billmeyer et al., Principles of Color Technology, 2nd Edition, Wiley and Sons, New York, 1981, Chapter 3. The a* value is a measure of reddish tone (positive a*) or greenish tone (negative a*). The b* value is a measure of bluish tone (negative b*) or yellowish tone (positive b*).
xe2x80x9cBlue-sensitivexe2x80x9d refers to sensitivity of the silver halide emulsion to a wavelength of from about 360 to about 540 nm, and preferably it refers to sensitivity to a wavelength of from about 380 to about 470 nm.
The term xe2x80x9cfully forehardenedxe2x80x9d is employed to indicate the forehardening of hydrophilic colloid layers to a level that limits the weight gain of a radiographic film to less than 120% of its original (dry) weight in the course of wet processing. The weight gain is almost entirely attributable to the ingestion of water during such processing.
In referring to grains and silver halide emulsions containing two or more halides, the halides are named in order of ascending molar concentrations.
The term xe2x80x9caspect ratioxe2x80x9d is used to define the ratio of tabular grain diameter to tabular grain thickness. Tabular grain diameter is calculated from a disc-centrifuge measurement and tabular grain thickness is determined from a reflectance measurement. Both measurements are performed using appropriate standards for calibration.
The term xe2x80x9ccovering powerxe2x80x9d is used to indicate 100 times the ratio of maximum density to developed silver measured in mg/dm2.
The term xe2x80x9cdual-coatedxe2x80x9d is used to define a radiographic film having silver halide emulsion layers disposed on both the front- and backsides of the support. The radiographic silver halide films used in the present invention are xe2x80x9cdual-coated.xe2x80x9d
The term xe2x80x9cfluorescent intensifying screenxe2x80x9d refers to a screen that absorbs X-radiation and emits light. A xe2x80x9cpromptxe2x80x9d emitting fluorescent intensifying screen will emit light immediately upon exposure to radiation while a xe2x80x9cstoragexe2x80x9d fluorescent screen can xe2x80x9cstorexe2x80x9d the exposing X-radiation for emission at a later time when the screen is irradiated with other radiation (usually visible light).
The terms xe2x80x9cfrontxe2x80x9d and xe2x80x9cbackxe2x80x9d refer to layers, films, or fluorescent intensifying screens nearer to and farther from, respectively, the source of X-radiation.
The term xe2x80x9crare earthxe2x80x9d is used to indicate chemical elements having an atomic number of 39 or 57 through 71.
Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North St., Emsworth, Hampshire P010 7DQ England. It is also available from Emsworth Design Inc., 147 West 24th Street, New York, N.Y. 10011.
The blue-sensitive radiographic silver halide films of this invention include a flexible support having disposed on both sides thereof, one or more photographic silver halide emulsion layers as described below and optionally one or more non-radiation sensitive hydrophilic layer(s). The silver halide emulsions in the various layers on both sides of the support can be the same or different.
In preferred embodiments, the photographic silver halide film has the same silver halide emulsion(s) on both sides of the support. It is also preferred that the film has a protective overcoat (described below) over the silver halide emulsions on each side of the support.
The support can take the form of any conventional radiographic film support that is X-radiation and light transmissive. Useful supports for the films of this invention can be chosen from among those described in Research Disclosure, September 1996, Item 38957 XV. Supports and Research Disclosure, Vol. 184, August 1979, Item 18431, XII. Film Supports.
The support is preferably a transparent film support. In its simplest possible form the transparent film support consists of a transparent film chosen to allow direct adhesion of the hydrophilic silver halide emulsion layers or other hydrophilic layers. More commonly, the transparent film is itself hydrophobic and subbing layers are coated on the film to facilitate adhesion of the hydrophilic silver halide emulsion layers. Typically the film support is either colorless or blue tinted (tinting dye being present in one or both of the support film and the subbing layers). Referring to Research Disclosure, Item 38957, Section XV Supports, cited above, attention is directed particularly to paragraph (2) that describes subbing layers, and paragraph (7) that describes preferred polyester film supports.
Polyethylene terephthalate and polyethylene naphthalate are the preferred transparent film support materials.
In the more preferred embodiments, at least one non-light sensitive hydrophilic layer is included with one silver halide emulsion layer on each side of the film support. This layer may be called an interlayer or overcoat, or both.
Each side of the support comprises one or more silver halide emulsion layers. On at least one of those sides (and preferably on both sides), at least one silver halide emulsion that contain predominantly tabular silver halide grains (that is, more than 60 weight % of all grains and preferably at least 80 weight %) having an average aspect ratio greater than 15. Preferably, these grains have an aspect ratio of from about 20 to about 30. The optimal aspect ratio may be dependent upon the particular mol % of iodide present in the grains.
The average thickness of these tabular silver halide grains is at least 0.1 xcexcm with an upper limit of 0.15 xcexcm, and preferably the tabular silver halide grain thickness is from about 0.10 to about 0.14 xcexcm.
These tabular silver halide grains particularly include predominantly (at least 90 mol %) bromide, preferably at least 95 mol % bromide, and more preferably at least 97 mol % bromide, based on total silver in the emulsion layer. In addition, these tabular grains have up to 4 mol % iodide, and preferably up to 3.5 mol % iodide, based on total silver in the emulsion layer. Preferably, the iodide content is at least 1 mol % and preferably at least 2 mol %, based on total silver in the emulsion layer. The tabular silver halide grains in each silver halide emulsion unit (or silver halide emulsion layers) can be the same or different, and there can be mixtures of tabular grains in an emulsion layer having different halide composition and aspect ratio as long as the conditions noted above are still met.
The silver halide emulsion layers on the opposing sides of the support are identified herein as xe2x80x9cfirstxe2x80x9d and xe2x80x9csecondxe2x80x9d silver halide emulsion layers with the xe2x80x9cfirstxe2x80x9d layer being disposed on the side of the film that is exposed first. Preferably, these xe2x80x9cfirstxe2x80x9d and xe2x80x9csecondxe2x80x9d silver halide emulsion layers have the same composition (for example, type of grains, grain halide composition, silver coverage, and hydrophilic polymeric vehicle mixture).
Thus, either or both of the first and second silver halide emulsion layers can have the same or different composition and comprise predominantly tabular silver halide grains that have an aspect ratio of at least 15, a grain thickness of at least 0.1 xcexcm, and comprise at least 90 mol % bromide and up to 4 mol % iodide, based on total silver halide, substantially all of the iodide being present in an internal localized portion of the tabular silver halide grains that excludes the surface of the grains,
wherein the tabular silver halide grains in the first and/or second silver halide emulsion layers are dispersed in a hydrophilic polymeric vehicle mixture comprising at least 0.5% of oxidized gelatin, based on the total dry weight of the polymeric vehicle mixture in the first and/or second emulsion layers, and
the tabular silver halide grains are spectrally sensitized with the combination of first and second spectral sensitizing dyes that described below.
Tabular grain emulsions that have the desired composition and sizes are described in greater detail in the following patents, the disclosures of which are incorporated herein by reference:
U.S. Pat. No. 4,414,310 (Dickerson), U.S. Pat. No. 4,425,425 (Abbott et al.), U.S. Pat. No. 4,425,426 (Abbott et al.), U.S. Pat. No. 4,439,520 (Kofron et al.), U.S. Pat. No. 4,434,226 (Wilgus et al.), U.S. Pat. No. 4,435,501 (Maskasky), U.S. Pat. No. 4,713,320 (Maskasky), U.S. Pat. No. 4,803,150 (Dickerson et al.), U.S. Pat. No. 4,900,355 (Dickerson et al.), U.S. Pat. No. 4,994,355 (Dickerson et al.), U.S. Pat. No. 4,997,750 (Dickerson et al.), U.S. Pat. No. 5,021,327 (Bunch et al.), U.S. Pat. No. 5,147,771 (Tsaur et al.), U.S. Pat. No. 5,147,772 (Tsaur et al.), U.S. Pat. No. 5,147,773 (Tsaur et al.), U.S. Pat. No. 5,171,659 (Tsaur et al.), U.S. Pat. No. 5,252,442 (Dickerson et al.), U.S. Pat. No. 5,370,977 (Zietlow), U.S. Pat. No. 5,391,469 (Dickerson), U.S. Pat. No. 5,399,470 (Dickerson et al.), U.S. Pat. No. 5,411,853 (Maskasky), U.S. Pat. No. 5,418,125 (Maskasky), U.S. Pat. No. 5,494,789 (Daubendiek et al.), U.S. Pat. No. 5,503,970 (Olm et al.), U.S. Pat. No. 5,536,632 (Wen et al.), U.S. Pat. No. 5,518,872 (King et al.), U.S. Pat. No. 5,567,580 (Fenton et al.), U.S. Pat. No. 5,573,902 (Daubendiek et al.), U.S. Pat. No. 5,576,156 (Dickerson), U.S. Pat. No. 5,576,168 (Daubendiek et al.), U.S. Pat. No. 5,576,171 (Olm et al.), and U.S. Pat. No. 5,582,965 (Deaton et al.).
The iodide present in the tabular silver halide grains described above is substantially all located in an xe2x80x9cinternal localized portionxe2x80x9d of the grains. This means that substantially none of the iodide is present on the surfaces of the grains. This feature can be defined by the volume % of a grain wherein 0 volume % refers to the center of the grain and 100 volume % refers to the grain surface. In the present invention, the iodide is present in an internal localized portion at from about 1.5% to about 90 volume %. Preferably, the xe2x80x9cbeginningxe2x80x9d of the internal localized portion is from about 1.5% to about 10 volume % and the xe2x80x9cendingxe2x80x9d of the internal localized portion is from about 65% to about 90 volume %. Thus, the nucleated internal portion of the grains contains no iodide. More preferably, the iodide is uniformly distributed throughout the internal localized portion represented by from about 1.7 to about 85 volume %.
This localization of the iodide within the tabular silver halide grains can be achieved using known procedures whereby preparation of the tabular silver halide grains is begun (nucleation and initial growth) without the presence of iodide. Then iodide is introduced during a predetermined portion of the manufacturing method until the desired volume % includes iodide, and manufacture of the grains is continued without iodide. A representative preparation is provided in the following paragraphs. Other details for making tabular grains in a similar manner are provided in U.S. Pat. No. 4,665,012 (Sugimoto et al.), incorporated herein by reference.
In general, the tabular grains useful in the practice of this invention can be prepared using a silver bromide-grain nucleation (and early growth) in a xe2x80x9cbromide ion concentration free-fallxe2x80x9d process with slow silver ion addition into a bromide ion-rich deionized oxidized gelatin environment. The number of grains having tabular morphology is enhanced using a brief period of silver solvent enhanced digestion. After digestion, additional gelatin of any type (preferably oxidized gelatin and preferably deionized oxidized gelatin) is added. Further grain growth is carried out by controlling the silver ion concentration in a halide-rich environment, using either bromide or iodobromide growth/control salts as required. Following grain growth, after washing out salts remaining in the solution phase of the emulsion, the emulsion is further peptized using a non-oxidized gelatin (such as deionized non-oxidized gelatin).
The silver halide emulsions described herein can have some non-tabular silver halide grains as long as they represent less than 40 weight % of the total grains in a given silver halide emulsion layer. Such grains can have any desirable morphology including, but not limited to, octahedral, tetradecahedral, rounded, spherical or other non-tabular or singularly-twinned or multiply-non-parallel twinned morphologies, or be comprised of a mixture of two or more of such morphologies.
A variety of silver halide dopants can be used, individually and in combination, to improve contrast as well as other common properties, such as speed and reciprocity characteristics. A summary of conventional dopants to improve speed, reciprocity and other imaging characteristics is provided by Research Disclosure, Item 38957, cited above, Section I. Emulsion grains and their preparation, sub-section D. Grain modifying conditions and adjustments, paragraphs (3), (4), and (5).
A general summary of silver halide emulsions and their preparation is provided by Research Disclosure, Item 38957, cited above, Section I. Emulsion grains and their preparation. After precipitation and before chemical sensitization the emulsions can be washed by any convenient conventional technique using techniques disclosed by Research Disclosure, Item 38957, cited above, Section III. Emulsion washing.
The emulsions can be chemically sensitized by any convenient conventional technique as illustrated by Research Disclosure, Item 38957, Section IV. Chemical Sensitization: Sulfur, selenium or gold sensitization (or any combination thereof) are specifically contemplated. Sulfur sensitization is preferred, and can be carried out using for example, thiosulfates, thiosulfonates, thiocyanates, isothiocyanates, thioethers, thioureas, cysteine or rhodanine. A combination of gold and sulfur sensitization is most preferred.
It is essential that the tabular silver halide grains used in the blue-sensitive radiographic films of this invention be spectrally sensitized using a combination of two different classes of spectral sensitizing dyes. This combination of first and second spectral sensitizing dyes provides a combined J-aggregate absorption within the range of from about 380 to about 500 nm (preferably from about 410 to about 490 nm) when absorbed on the tabular silver halide grains. The two dyes typically have different maximum absorption and thus, one is generally xe2x80x9clowerxe2x80x9d than the other dye. This xe2x80x9clowerxe2x80x9d dye is termed herein the xe2x80x9cfirstxe2x80x9d spectral sensitizing dye and has a maximum J-aggregate absorption of from about 20 to about 50 nm lower than the maximum J-aggregate absorption of the second (xe2x80x9chigherxe2x80x9d) spectral sensitizing dye.
Multiple spectral sensitizing dyes of each type can be used if desired. Thus, two or more first spectral sensitizing dyes can be used with one or more second spectral sensitizing dyes, and the converse is also true. Preferably, only one of each type of spectral sensitizing dye is used in the present invention.
The molar ratio of the first spectral sensitizing dye to the second spectral sensitizing dye is from about 0.25:1 to about 1:1, and preferably it is from about 0.3:1 to about 0.8:1. The most preferred molar ratio is from about 0.4:1 to about 0.7:1. In addition, the combination of spectral sensitizing dyes is present in the silver halide emulsion containing the tabular silver halide grains in an amount sufficient to provide from about 50 to about 100% (preferably from about 70 to about 80%) of saturation coverage of the tabular silver halide grains. For most of the useful blue-light sensitive spectral sensitizing dyes, this would amount to from about 400 to about 800 mg/mole, or from about 0.55 to about 1.1 mmol/mole, of total silver in the silver halide emulsion layer. The particular amount with vary with the surface area of the tabular grains used in the emulsion. Optimum amounts will vary with the particular dyes used and a skilled worker in the art would understand how to achieve optimal results with the combination of dyes in appropriate amounts. Obviously, the spectral sensitizing dyes may also be absorbed to any silver halide grains that are not tabular in morphology.
In general, the first spectral sensitizing dye is an anionic benzimidazole-benzoxazole carbocyanine having at least one sulfo or carboxy group in the molecule, and the second spectral sensitizing dye is an anionic benzothiazole-benzothiazole carbocyanine having at least one sulfo or carboxy group in the molecule. Preferably, each of the first and second spectral sensitizing dyes has at least two sulfo groups in the molecule.
More particularly, the first spectral sensitizing dye is a monomethine carbocyanine dye represented by the following Structure I: 
wherein Z1 and Z2 represent the carbon atoms necessary to form a substituted or unsubstituted benzene or naphthalene ring. Thus, the terms xe2x80x9cbenzothiazolexe2x80x9d, xe2x80x9cbenzoxazolexe2x80x9d, and xe2x80x9cbenzimidazolexe2x80x9d used herein to define the spectral sensitizing dyes are intended to include compounds where Z1 and Z2 form naphthalene rings fused to the defined N-containing heterocyclic rings. Preferably, each of Z1 and Z2 independently represent the carbon atoms necessary to form a substituted or unsubstituted benzene ring.
In Structure I, R1, R2, and R3 are independently alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms in the aromatic ring, alkenyl groups having 2 to 8 carbon atoms, and other substituents that would be readily apparent to one skilled in the art. Such groups can be substituted with one or more hydroxy, alkyl, carbonamido, carboxy, sulfo, halo, and alkoxy groups. Preferably, at least one of the R1, R2, and R3 groups comprises at least one sulfo or carboxy group.
More preferably, R1, R2, and R3 are independently alkyl groups having 1 to 4 carbon atoms, phenyl groups, alkoxy groups having 1 to 4 carbon atoms, or alkenyl groups having 2 to 4 carbon atoms. All of these groups can be substituted as described above, and in particular, they can be substituted with a sulfo group.
R6 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a phenyl group, each of which groups can be substituted as described above for the other radicals. Preferably, R6 is hydrogen, or a methyl or ethyl group.
In Structure I, X1 is a suitable anion or cation, as needed, to balance the charge of the dye molecule. Useful anions include, but are not limited to, halides, thiocyanate, sulfate, perchlorate, p-toluene sulfonate, ethyl sulfate, and other anions readily apparent to one skilled in the art. Suitable cations include, but are not limited to, alkali metal ions.
Particularly useful second spectral sensitizing dyes are monomethine cyanine dyes represented by the following Structure (II): 
wherein Z1 and Z2 represent the carbon atoms necessary to form a substituted or unsubstituted benzene or naphthalene ring (as defined above for Structure I) and R4 and R5 are independently substituted or unsubstituted alkyl, alkoxy, aryl, or alkenyl groups as defined above for R1 through R3. R6 is as defined above for Structure I. X2 is a suitable anion or cation as defined above for X1.
Preferably, R4 and R5 are independently alkyl groups having 1 to 4 carbon atoms, phenyl groups, alkoxy groups having 1 to 4 carbon atoms, or alkenyl groups having 2 to 4 carbon atoms.
Representative first spectral sensitizing dyes include the following Dyes I-1 through I-7, and representative second spectral sensitizing dyes include the following Dyes II-1 through II-10. A combination of Dyes I-1 and II-1 is most preferred in the practice of this invention. 
The spectral sensitizing dyes described herein can be prepared as described in U.S. Pat. No. 4,518,689 (Noguchi et al.), incorporated herein by reference, or by using known starting materials and synthetic procedures. Other details about such compounds are provided by Hamer, The Cyanine Dyes and Related Compounds, Interscience, New York, 1964.
Instability that increases minimum density in negative-type emulsion coatings (that is fog) can be protected against by incorporation of stabilizers, antifoggants, antikinking agents, latent-image stabilizers and similar addenda in the emulsion and contiguous layers prior to coating. Such addenda are illustrated by Research Disclosure, Item 38957, Section VII. Antifoggants and stabilizers, and Item 18431, Section II: Emulsion Stabilizers, Antifoggants and Antikinking Agents.
It may also be desirable that one or more silver halide emulsion layers include one or more covering power enhancing compounds adsorbed to surfaces of the silver halide grains. A number of such materials are known in the art, but preferred covering power enhancing compounds contain at least one divalent sulfur atom that can take the form of a xe2x80x94Sxe2x80x94 or xe2x95x90S moiety. Such compounds include, but are not limited to, 5-mercapotetrazoles, dithioxotriazoles, mercapto-substituted tetraazaindenes, and others described in U.S. Pat. No. 5,800,976 (Dickerson et al.) that is incorporated herein by reference for the teaching of the sulfur-containing covering power enhancing compounds.
The silver halide emulsion layers and other hydrophilic layers on both sides of the support of the radiographic films generally contain conventional polymer vehicles (peptizers and binders) that include both synthetically prepared and naturally occurring colloids or polymers. Conventional gelatino-vehicles and related layer features are disclosed in Research Disclosure, Item 38957, Section II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda. The emulsions themselves can contain peptizers of the type set out in Section II, paragraph A. Gelatin and hydrophilic colloid peptizers. The hydrophilic colloid peptizers are also useful as binders and hence are commonly present in much higher concentrations than required to perform the peptizing function alone.
Cationic starch used as a peptizer for tabular grains is described in U.S. Pat. No. 5,620,840 (Maskasky) and U.S. Pat. No. 5,667,955 (Maskasky). Both hydrophobic and hydrophilic synthetic polymeric vehicles can be used also. Such materials include, but are not limited to, polyacrylates (including polymethacrylates), polystyrenes and polyacrylamides (including polymethacrylamides). Dextrans can also be used. Examples of such materials are described for example in U.S. Pat. No. 5,876,913 (Dickerson et al.), incorporated herein by reference.
It is essential that the coated tabular grain silver halide emulsion layers, on one or both sides of the support, comprise tabular silver halide grains dispersed in a hydrophilic polymeric vehicle mixture comprising at least 0.5% and preferably at least 0.8% of oxidized gelatin based on the total weight of polymeric vehicle mixture in that coated emulsion layer. The upper limit for the oxidized gelatin is not critical but for practical purposes it is 1.5% based on the total weight of the polymer vehicle mixture. Preferably, from about 0.8 to about 1.2% (by weight) of the polymer vehicle mixture is oxidized gelatin.
It is also preferred that the oxidized gelatin is in the form of deionized oxidized gelatin but non-deionized oxidized gelatin can be used, or a mixture of deionized and non-deionized oxidized gelatins can be used. Deionized oxidized gelatin generally has the property of relatively lower amounts of methionine per gram of gelatin than other forms of gelatin. Preferably, the amount of methionine is from 0 to about 3 xcexcmol of methionine, and more preferably from 0 to 1 xcexcmol of methionine, per gram of gelatin. This material can be prepared using known procedures.
The remainder of the polymeric vehicle mixture can be any of the hydrophilic vehicles described above, but preferably it is composed of alkali-treated gelatin, acid-treated gelatin acetylated gelatin, or phthalated gelatin.
The silver halide emulsions containing the tabular silver halide grains described above can be prepared as noted using a considerable amount of oxidized gelatin (preferably deionized oxidized gelatin) during grain nucleation and growth, and then additional polymeric binder of any type can be added to provide the coating formulation. The amounts of oxidized gelatin in the emulsion can be as low as 0.3 g per mole of silver and as high as 27 g per mole of silver in the emulsion. Preferably, the amount of oxidized gelatin in the emulsion is from about 1 to about 20 g per mole of silver.
The silver halide emulsion layers (and other hydrophilic layers) in the radiographic films are generally fully hardened using one or more conventional hardeners. Thus, the amount of hardener in each silver halide emulsion and other hydrophilic layer is generally at least 0.6% and preferably at least 0.7%, based on the total dry weight of the polymer vehicle in each layer.
Conventional hardeners can be used for this purpose, including but not limited to formaldehyde and free dialdehydes such as succinaldehyde and glutaraldehyde, blocked dialdehydes, xcex1-diketones, active esters, sulfonate esters, active halogen compounds, s-triazines and diazines, epoxides, aziridines, active olefins having two or more active bonds, blocked active olefins, carbodiimides, isoxazolium salts unsubstituted in the 3-position, esters of 2-alkoxy-N-carboxydi-hydroquinoline, N-carbamoyl pyridinium salts, carbamoyl oxypyridinium salts, bis(amidino) ether salts, particularly bis(amidino) ether salts, surface-applied carboxyl-activating hardeners in combination with complex-forming salts, carbamoylonium, carbamoyl pyridinium and carbamoyl oxypyridinium salts in combination with certain aldehyde scavengers, dication ethers, hydroxylamine esters of imidic acid salts and chloroformamidinium salts, hardeners of mixed function such as halogen-substituted aldehyde acids (for example, mucochloric and mucobromic acids), onium-substituted acroleins, vinyl sulfones containing other hardening functional groups, polymeric hardeners such as dialdehyde starches, and poly(acrolein-co-methacrylic acid).
The levels of silver and polymer vehicle in the radiographic silver halide film of the present invention are as follows. In general, the total amount of silver on each side of the support is at least 17 and no more than 21 mg/dm2 in one or more emulsion layers. Preferably, the amount of silver on each side of the support is from about 17 to about 19 mg/dm2. In addition, the total amount of polymer vehicle on each side of the support is generally at least 22 and no more than 30 mg/dm2 in one or more hydrophilic layers. The amounts of silver and polymer vehicle on the two sides of the support in the radiographic silver halide film can be the same or different. These amounts refer to dry weights.
The radiographic silver halide films of this invention generally include a surface protective overcoat on each side of the support that typically provides physical protection of the emulsion layers. Each protective overcoat can be sub-divided into two or more individual layers. For example, protective overcoats can be sub-divided into surface overcoats and interlayers (between the overcoat and silver halide emulsion layers). In addition to vehicle features discussed above the protective overcoats can contain various addenda to modify the physical properties of the overcoats. Such addenda are illustrated by Research Disclosure, Item 38957, Section IX. Coating physical property modifying addenda, A. Coating aids, B. Plasticizers and lubricants, C. Antistats, and D. Matting agents. Interlayers that are typically thin hydrophilic colloid layers can be used to provide a separation between the emulsion layers and the surface overcoats. The overcoat on at least one side of the support can also include a blue toning dye or a tetraazaindene (such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) if desired.
The protective overcoat is generally comprised of one or more hydrophilic colloid vehicles, chosen from among the same types disclosed above in connection with the emulsion layers. Protective overcoats are provided to perform two basic functions. They provide a layer between the emulsion layers and the surface of the film for physical protection of the emulsion layer during handling and processing. Secondly, they provide a convenient location for the placement of addenda, particularly those that are intended to modify the physical properties of the radiographic film.
The various coated layers of radiographic silver halide films of this invention can also contain tinting dyes to modify the image tone to transmitted or reflected light. These dyes are not decolorized during processing and may be homogeneously or heterogeneously dispersed in the various layers. Preferably, such non-bleachable tinting dyes are in a silver halide emulsion layer.
The radiographic imaging assemblies of the present invention comprise a blue-sensitive radiographic silver halide film of this invention and one or more fluorescent intensifying screens that emit radiation having a maximum absorption at from about 300 to about 540 nm (preferably from about 360 to about 500 nm). These screens can take any convenient form providing they meet all of the usual requirements for use in radiographic imaging. Examples of conventional, useful fluorescent intensifying screens and methods of making them are provided by Research Disclosure, Item 18431, cited above, Section IX. X-Ray Screens/Phosphors, and U.S. Pat. No. 5,021,327 (Bunch et al.), U.S. Pat. No. 4,994,355 (Dickerson et al.), U.S. Pat. No. 4,997,750 (Dickerson et al.), and U.S. Pat. No. 5,108,881 (Dickerson et al.), the disclosures of which are here incorporated by reference. The fluorescent layer contains phosphor particles and a binder, optimally additionally containing a light scattering material, such as titania or light absorbing materials such as particulate carbon, dyes or pigments. Any conventional binder (or mixture thereof) can be used but preferably the binder is an aliphatic polyurethane elastomer or another highly transparent elastomeric polymer.
Any conventional or useful phosphor can be used, singly or in mixtures, in the intensifying screens used in the practice of this invention as long as the emitting radiation has the desired wavelength. For example, useful phosphors are described in numerous references relating to fluorescent intensifying screens, including but not limited to, Research Disclosure, Vol. 184, August 1979, Item 18431, Section IX, X-ray Screens/Phosphors.
Suitable phosphors are described in U.S. Pat. No. 4,835,397 (Arakawa et al.) and U.S. Pat. No. 5,381,015 (Dooms), both incorporated herein by reference, and including for example divalent europium and other rare earth activated alkaline earth metal halide phosphors and rare earth element activated rare earth oxyhalide phosphors. Of these types of phosphors, the more preferred phosphors include alkaline earth metal fluorohalide prompt emitting and/or storage phosphors [particularly those containing iodide such as alkaline earth metal fluorobromoiodide storage phosphors as described in U.S. Pat. No. 5,464,568 (Bringley et al.), incorporated herein by reference].
Another class of useful phosphors includes rare earth hosts such as rare earth activated mixed alkaline earth metal sulfates such as europium-activated barium strontium sulfate.
A representative fluorescent intensifying screen useful in the present invention is commercially available as Fuji Film HighPlus Screens that include calcium tungstate as the phosphor.
A particularly useful fluorescent intensifying screen can be prepared using an alkaline earth fluorohalide phosphor and especially a rare earth activated (doped) alkaline earth fluorohalide phosphor. An europium activated barium fluorohalide phosphor is most preferred.
Exposure and processing of the radiographic silver halide films of this invention can be undertaken in any convenient conventional manner. The exposure and processing techniques of U.S. Pat. No. 5,021,327 and U.S. Pat. No. 5,576,156 (both noted above) are typical for processing radiographic films. Other processing compositions (both developing and fixing compositions) are described in U.S. Pat. No. 5,738,979 (Fitterman et al.), U.S. Pat. No. 5,866,309 (Fitterman et al.), U.S. Pat. No. 5,871,890 (Fitterman et al.), U.S. Pat. No. 5,935,770 (Fitterman et al.), U.S. Pat. No. 5,942,378 (Fitterman et al.), all incorporated herein by reference. The processing compositions can be supplied as single- or multi-part formulations, and in concentrated form or as more diluted working strength solutions.
It is particularly desirable that the radiographic silver halide films be processed within 90 seconds (xe2x80x9cdry-to-dryxe2x80x9d) and preferably within 60 seconds (for a minimum of at least 20 seconds), for the developing, fixing, any washing (or rinsing) and drying steps. Such processing can be carried out in any suitable processing equipment including but not limited to, a Kodak X-OMAT(trademark) RA 480 processor that can utilize Kodak Rapid Access processing chemistry. Other xe2x80x9crapid access processorsxe2x80x9d are described for example in U.S. Pat. No. 3,545,971 (Barnes et al.) and EP 0 248,390A1 (Akio et al.). Preferably, the black-and-white developing compositions used during processing are free of any gelatin hardeners, such as glutaraldehyde.
Since rapid access processors employed in the industry vary in their specific processing cycles and selections of processing compositions, the preferred radiographic films satisfying the requirements of the present invention are specifically identified as those that are capable of dry-to-dye processing according to the following reference conditions:
Any additional time is taken up in transport between processing steps. Typical black-and-white developing and fixing compositions are described in the Example below.
Radiographic kits can include a radiographic film or imaging assembly of this invention, one or more additional fluorescent intensifying screens and/or metal screens, and/or one or more suitable processing compositions (for example black-and-white developing and fixing compositions).